Hair bleach containing a thiocyanate catalyst

ABSTRACT

A BLEACH FOR HUMAN HAIR, IN AQUEOUS EMULSION FORM, WHICH SAFELY AND QUICKLY BLEACHES THE HAIR, INCLUDES, AS ACTIVE BLEACHING CONSTITUENTS, A MIXTURE OF PRE-COMPOUND, E.G., SODIUM PERSULFATE, AMMONIUM PERSULFATE, SODIUM CARBONATE PEROXIDE, AND HYDROGEN PEROXIDE A CATALYST FOR AIDING THE RELEASE OF OOXYGEN FROM SUCH MATERIALS, E.G., AMMONIUM THIOCYANATE, WATER AND EMULSIFYING MATERIALS, E.G., AMMONIUM OLEATE. THE BLEACHING COMPOSITION IS PREPARED SHORTLY BEFORE USE BY QUICKLY COMBINING AT LEAST PARTIALLY PRE-MIXED PORTIONS THEREOF AND IS APPLIED PROMPTLY TO THE HAIR TO BE BLEACHED, ON WHICH THE COMPOSITION FORMS A FOAM OF LIMITED HEIGHT AND OF A SUFFICIENT VISCOSITY TO HOLD IN CONTACT WITH THE HAIR THE BLEACHING CONSTITUENTS AND OXYGEN RELEASED.

United States Patent Oflce Patented July 9, 1974 3,823,231 HAIR BLEACHCONTAINING A THIOCYANATE CATALYST Frank P. Bucaria, 1952 Sweet HomeRoad, Williamsville, N.Y. 14221 No Drawing. Filed Apr. 20, 1971, Ser.No. 135,759 Int. Cl. A61k 7/12 US. Cl. 424-62 7 Claims ABSTRACT OF THEDISCLOSURE A bleach for human hair, in aqueous emulsion form, whichsafely and quickly bleaches the hair, includes, as active bleachingconstituents, a mixture of pre-compounds, e.g., sodium persulfate,ammonium persulfate, sodium carbonate peroxide, and hydrogen peroxide, acatalyst for aiding the release of oxygen from such ma terials, e.g.,ammonium thiocyanate, water and an emulsifying material, e.g., ammoniumoleate. The bleaching composition is prepared shortly before use byquickly combining at least partially pre-mixed portions thereof and isapplied promptly to the hair to be bleached, on which the compositionforms a foam of limited height and of a suflicient viscosity to hold incontact with the hair the bleaching constituents and oxygen released.

INTRODUCTION This invention relates to the bleaching of human hair andto compositions for effecting such bleaching. Products of the inventionoperate at substantially neutral pHs and steadily release bleachingoxygen, so that bleaching is obtained without harm to the hair. Theinvention also relates to methods of making bleaching compositions andof effecting bleaching of hair with them.

BACKGROUND OF THE INVENTION For many years the most effective andpopular of bleaches for the human hair has been hydrogen peroxide,usually employed in an aqueous solution. Oxygen is readily released fromsuch solutions at high pI-Is. Generally, commercial aqueous hydrogenperoxides are of 3 to 6% oxygen content, which is ordinarily high enoughto result in effective bleaching of the hair. Such bleaching isundertaken before the application of dyes, such as those employed togive the hair desired light colors or shades. In some instances,hydrogen peroxide has been incorporated into shampoos or emulsions forthe hair, which may contain higher fatty acid soaps, such as the saltsof oleic acid. Various per-compounds have been employed to generateoxygen for bleaching and it is known that the release of oxygen fromsuch compounds can be accelerated with catalysts for this puropse.However, although various components of the present composition areknown in the bleach art, applicant does not know of any of the inventedcombinations of required components of the present invention that havepreviously been made and would result in compositions having theproperties of those of this invention.

DESCRIPTION OF THE INVENTION The products and processes of thisinvention enable one to obtain a fast, steady bleaching, utilizing athickened composition of limiting foaming power, at a substantiallyneutral pH. Thus, little harm is done to the hair by the bleachingoperation and it is of greater strength and luster after bleaching thanit would be after the use of harsher bleaches of higher alkalinities.Because the hair is not deteriorated by application of the presentbleaches, it has been found that various dyes applied to it, such as theparaphenylene dyes, are more substantive and are less easily removed bywater and shampooing than is the case when the dyes are applied afterregular hydrogen peroxide bleaching.

In accordance with the present invention a bleach for human haircomprises a per-compound capable of releasing oxygen from aqueoussolution upon being contacted with a catalyst, hydrogen peroxide, waterand a thiocyanate catalyst, which catalyzes the release of oxygen fromthe per-compound at a pH in the range of 6.5 to 8.5. In preferredbleaches there are present certain proportions of sodium carbonateperoxide, sodium persulfate, ammonium persulfate, hydrogen peroxide,water and ammonium thiocyanate. Examples of some important additives tothe basic formula include amonium oleate, t-octyl phenoxy polyethoxyethanol, oleyl alcohol, propylene glycol, methanol and sodium sulfite.

The described compositions are made by mixing separately, shortly beforeintended use, (A) the per-compounds and an aqueous solution of hydrogenperoxide, (B) the thiocyanate, nonionic detergent, oleic acid, ammoniumhydroxide, oleyl alcohol, propylene glycol and methanol, and (C)admixing the two mixtures described. In use, a creamy aqueous emulsioncomprising the various described constituents is applied to the hairpromptly after being made and is held on it for a period from 15 to 45minutes at a substantially neutral pH, after which it is rinsed off WithWater, leaving excellently bleached the hair to which it has beenapplied. Of course, although it is preferred to make the bleach by sucha mixing of components, other orders of addition and other pre-mixes maybe employed so long as the final bleach contains the desiredingredients. Additionally, it is preferred that the bleach be used soonafter combination of the materials thereof, usually within five minutesof completion of the emulsion and preferably, within 30 seconds or aminute or two.

The per-compounds or per-salts used include primarily sodium carbonateperoxide (2Na CO -3H O or other suitable alkali metal or other carbonateperoxide, e.g., potassium carbonate peroxide. In place of the carbonateperoxide one may employ percarbonates, e.g., sodium percarbonate. Thepersulfates include principally sodium persulfate, although other alkalimetal persulfates and other persulfates may be employed, and ammoniumpersulfate is generally present to supplement the action of the sodiumpersulfate. The persulfates or equivalents or derivatives thereof areusually packed together as a mixed powder, with a small quantity ofsodium sulfite, as a desiccant-stabilizer, and are protected frommoisture and air by a sealed aluminum barrier, as in a heat sealedpouch, preferably sealed under vacuum. The alkali metal carbonateperoxide or percarbonate is packed separately in similar manner, alsowith the sodium sulfite to protect it.

The hydrogen peroxide employed, While it may be of any suitableconcentration in water, will usually be in the 1.5 to 18% range,preferably from 2 to 10%, and most preferably, will be either 3 or 6% inwater, corresponding to 10 or 20 volumes of oxygen obtainable. In mostof the presently described compositions 6% peroxide is employed. The H 0is usually stabilized against premature release of oxygen, with a smallamount of a stabilizing chemical, e.g., phenacetin.

Except for the thiocyanate catalyst, the rest of the bleach is usually aliquid solution (preferable) or an emulsion. It comprises a suitablesoap, usually unsaturated and of 12 to 18 carbon atoms. Such soap, whichmay be an alkali metal soap, is preferably ammonium, amine oralkanolamine oleate and of these the ammonium oleate is considered to bethe best. The soap is made by the reaction of oleic acid orcorresponding higher fatty acid and a suitable base. Thus, to makeammonium oleate, there will be employed ammonia, generally as a 28%solution in water, and oleic acid. These may be heated to promotereaction but usually will sufficiently react in solution, whether thatsolution be aqueous or alcoholic. pH adjustments may be assisted byutilizing an excess of either the ammonia or oleic acid. Althoughammonia gas may be employed in the production of the ammonium oleate orammonium oleate might be utilized directly, it is preferred to react anaqueous solution of ammonium hydroxide with the oleic acid. Then too,while 28% ammonia is the standard ammonium hydroxide solution used,various other percentages, usually from 5 to 28% can be successfullyemployed. Oleyl alcohol or other higher fatty alcohol, preferablyunsaturated and of 16 to 18 carbon atoms, may be present with the oleicacid when it is neutralized by the ammonium hydroxide, or may be addedafterward. Usually it is preferred to have the oleic acid dissolved in alower alcohol, such as methanol or isopropanol, and lower alkyleneglycol such as propylene glycol, butylene glycol, or low molecularweight (of molecular weight less than about 300) polyethylene orpolypropylene glycol may be present with the alcohols. In addition tothe higher fatty acid soap, it is usually preferable to have present anonionic detergent which contains, as a hydrophilic group, a poly-loweralkoxy lower alkanol, such as polyethoxy ethanol, attached to ahydrophobic group which is preferably hydrocarbyloxy, such as higheralkyloxy or middle alkylphenoxy. By higher alkyl is meant an alkyl of 12to 18 carbon atoms and by middle alkyl is described one of 7 to 9 carbonatoms. The preferred nonionic detergent is of the Triton X-lOO type,which is t-octylphenoxy polyethoxy ethanol wherein the polyethoxyethanol portion is of 8 to 9 (ethoxy-l-ethanol) groups. Suitablevariations of such compounds are those wherein the polyethoxy ethanolportion or poly-lower alkoxy lower alkanol portion is about 60 to 70% byweight of the nonionic detergent. Other useful nonionics include theNeodols, Pluronics, Ucons and other polylower alkoxy alkanol detergents.

The catalyst which is used for promoting and controlling release ofoxygen or hydrogen peroxide from the per-compounds is a thiocyanate.Although alkali metal and other thiocyanates and complexes containingsuch materials may be utilized, at least to a partial extent, the mostpreferred thiocyanatc is ammonium thiocyanate. This will be packedseparately from the rest of the bleach constituents. Preferably, it andthe separate per-compound mixtures will be packed in desired usequantities. The hydrogen peroxide and the soap-detergent or diluentcompositions may also be packed in sufiicient quantities for a singleuse or may be measured out from containers which hold enough for severalbleaching operations. In preferred bleaching kits the user will supplyhis own hydrogen peroxide solution.

The water employed, if any is used, will preferably be deionized water,although distilled water and tap water of less than 100 parts permillion equivalent hardness, as calcium carbonate, may be verysuccessfully used and harder waters, although not preferred, result inoperative compositions. Often, the water will accompany otheringredients.

Of course, various adjuvants may be present in the compositions to givethem specially desirable properties. For example, perfumes, coloringagents, including dyes and dispersible pigments, emollients,bactericides, fungicides, stabilizers, pH regulating agents, e.g.,buffers, solvents, salts, carriers, e.g., powders, and other adjuvantsmay be employed but the totals thereof will normally not exceed about20% of the composition and preferably will be held to about 10% thereof,with individual adju vants rarely exceeding 5% of the composition(except for the carriers, which can be present in greater proportions)and preferably being less than 2% thereof.

The proportions of the various compounds present should be withincertain ranges for best results. Thus, it is highly preferred to utilizeabout 5 to parts of the nonionic detergent, about 20 to 45 parts ofsoap, about 5 to 10 parts of higher fatty alcohol, about 1 to 5 parts oflower alkylene glycol, about 5 to 15 parts of lower alkanol, about 10 to25 parts alkali metal carbonate peroxide, about 15 to 35 parts of alkalimetal persulfate, about 4 to 10 parts of ammonium persulfate, about 4 to11 parts of hydrogen peroxide, about to parts of water and about 0.4 to1.1 parts of thiocyanate catalyst.

Although the mixing together of the final bleaching composition willtake place only shortly before intended use, the pre-mixes made orvariations of them may, for convenience, be produced long before themixing of the hydrogen peroxide, the other per-compounds, the catalystand the diluent materials. Both the final and earlier mixings may takeplace at temperatures within the range of 15 C. to 60 C. but it will bemuch preferred to use temperatures within the range of 20 C. to 40 C.and in most instances room temperature, about 20 C. to 30 C., will beemployed. Reactions between the chemicals will usually raise thetemperature.

To use the bleaches after final mixing of the components or pre-mixedportions thereof, is a simple matter. Because the formulations will havebeen compounded so that the various constituents are properly balancedfor good bleaching effects, only the ordinary bleach application methodsnormally followed need be used. Thus, the hair will preferably be cleanbefore bleaching, with most of the oil and dirt having previously beenremoved from it by shampooing. With the hair still wet or damp, thebleach composition may be applied. Usually, from 20 to 400 ml. of theemulsion and preferably from 50- to 300 ml. thereof will be sufiicientto bleach the average head of hair but other quantities may also beused, depending largely on the length of the hair and the extent ofbleaching desired. Thus, when it is wanted that only the roots bebleached, less bleaching composition may be employed than when theentire head of hair is to be treated. If desired, the bleachingcomposition may be diluted With water before use but this is notnecessary. Also, the hair may be bleached successfully without previouswashing and can be dry before bleaching. Frosted bleaching effects arealso obtainable.

When applied to the entire head of hair, the desired amount of bleachingcomposition, e.g., 200 to 300 cc., either diluted or not, is poured ontothe hair and distributed throughout it. To obtain the most evenbleaching this is done quickly, usually within a minute or two. Whenonly the roots are being bleached, the hair is parted in the usual way,bleach is applied to the exposed hair, and the partings and applicationsare continued, usually at V2 to 1 inch intervals, until all the rootareas have had bleach applied to them. This might take from 1 to fiveminutes but the faster applications are preferred, providing that theyare even. The bleach emulsion is thick and covers the scalp to a depthof about 3 mm. when first applied, expanding to from 10 to 25 mm. asoxygen is generated. The temperature of the hair and bleach solu tion,when applied, Will usually be about room temperature, 20 to 40 C. butother suitable temperatures for particular conditions may be used. ThepH of the bleach solution or emulsion applied will usually be from about6.5 to 8.5, preferably from 6.8 to 7.5. At such pHs good bleaching iseffected gradually and hair damage during bleaching is minimized. Theentire bleaching operation usually takes from 15 to 45 minutes butpreferably will take from 20 to 35 minutes and most preferably, from 20to 30 minutes. The bleach will be used or use will be begun immediatelyafter the composition has been prepared, generally within 30 seconds toa minute after such preparation. To avoid waste of bleaching power dueto loss of oxygen, the bleach will be compounded rapidly too, usuallywithin the mentioned time periods.

It is a feature of this invention that the bleaching composition appliedis of desired thickness and foaming characten'stics so that it does notdrip off the hair and does not foam into areas of the hair which it maybe desired to leave unbleached, as when only root sections of the hairare being treated. Thus, despite the generation of a gas, oxygen, fromthe bleaching composition, the height of the foam developed iscontrollable and may be limited to /2 or 1 inch in height, so thatbleaching will not extend beyond such distances from the roots, or willnot extend into areas of the hair where bleaching is not to be effected.

After the desired degree of bleaching has been obtained furtherbleaching can be halted by quick rinsing off of the bleaching materialsand drying of the hair. Dyeing may then be undertaken or, if desired,may sometimes be done on the wet or damp hair, without preliminarydrying. After the present bleaching treatments, the hair is bleachedwhite but is still lustrous and strong. Examination under a microscopeshows it to be less porous, with fewer split hairs and other signs ofstructural damage than hair bleached with ordinary high alkalinitybleaches. It takes dyeing and the dyes applied, particularly theparaphenylene dyes, are substantively held to the hair and are notreadily washed off it.

The various components of the present products each perform importantfunctions, resulting in the superior products and treatments described.Of course, the hydrogen peroxide releases bleaching oxygen, as do thesodium carbonate peroxide and the persulfates. Releases of oxygen aresteady, due to the balance of per-compounds and hydrogen peroxide,coupled with the catalytic action of the thiocyanate. The sodiumpersulfate, ammonium persulfate and sodium carbonate peroxide releasetheir oxygen contents at separate times and the hydrogen peroxidereleases rather steadily, with the result being a steady release ofbleaching power. The combination of oleic acid or ammonium oleate andoleyl alcohol with water produces the desired emulsion, which issufficiently thick or viscous so as not to run off the hair afterapplication. The ammonia neutralizes the oleic acid and adjusts theproduct pH. It may also help to catalyze release of oxygen from thehydrogen peroxide. The balance of ammonia and oleic acid may be adjustedto provide for the presence in the bleaching composition of an excess ofeither the base or the acid but generally approximately stoichiometricquantities will be used to make a neutral salt. The water and methanolpresent act as solvents and media for the emulsion or solution made. Thesodium carbonate peroxide and persulfates, in addition to providingoxygen for bleaching, also help to regulate the temperature of thebleach on the hair. In this respect, the ammonium persulfate tends tohold the temperature down, under 50 C., and preferably, under 40 C.,most preferably at about body temperature, e.g., 37 or 38 C. Theammonium thiocyanate catalyst, in addition to slowly releasing oxygenfrom the peroxide and persulfates during bleaching, also helps to removeiron colorants from the hair, on which they may be present, eitherphysically held to the hair shafts or associated with the melaninpigment thereof. The propylene glycol acts as a dispersing agent in thecompositions and helps to keep the foam from overdeveloping on the hair.The methanol and Triton X-100 also act to thin the emulsion, limitexcessive foaming and contribute surface tension lowering properties topromote better contact with the hair and promote more eflicientbleaching use of the oxygen developed. The methanol thins the oleatesoap so as to make it readily pourable and yet, after at least partialevaporation, allows it to be thickened on the hair, trapping oxygen asbubbles in the continuous phase.

As is seen from the above description, each of the components of theinvention contributes its function to the success of the inventedbleaching composition. In combination, they make a product which, aspackaged, is stable to storage, with shelf storage for over a year beingpossible with commercially useful formulas, and which releases bleachingactive ingredient at a satisfactory, regular rate and at an acceptablepH and temperature. The bleaching takes place over a reasonable timeperiod and at the end of that period the active oxygen component of thebleach is consumed. The product is of correct viscosity to remain on thehair without dripping and it does not foam excessively, despite thefoam-generating action which would be expected due to oxygendevelopment. Yet, the generated oxygen is held in contact with the hairfor a sufficiently long time to bleach it effectively. Additional- 1y,iron removal or sequestration is effected by one of the components usedprimarily for a different, catalytic effect, and the iron so taken fromthe hair helps to regulate or speed the release of bleaching oxygen fromthe peroxide. All this is done by the described product without injuringthe hair, unlike prior art high alkalinity bleaching methods.

The following examples illustrate the invention. Of course, they do notlimit it. Unless otherwise indicated, all parts given in the formulasare by weight and all temperatures are in degrees Centigrade.

EXAMPLE 1 Parts by weight C7 9 alkyl phenoxy polyethoxy ethanol (60- 70%polyethoxy ethanol) 5 to 15 Ammonium oleate 20 to 45 Oleyl alcohol 5 to10 Propylene glycol 1 to 5 Methanol 5 to 15 Sodium carbonate peroxide 10to 25 Sodium persulfate 15 to 35 Ammonium persulfate 4 to 10 Hydrogenperoxide 4 to 11 Water 100.to 150 Ammonium thiocyanate 0.4 to 1.1 Sodiumsulfite 0.01 to 0.2

With the various mixing operations being effected at room temperature,about 25 C., a hair retouch bleaching kit is made, comprising fourparts, as follows:

Part A: Parts by weight C7 9 alkyl phenoxy polyethoxy ethanol (60-70%polyethoxy ethanol) 5 to 15 Methanol 5 to 15 Propylene glycol 1 to 15Oleyl alcohol 5 to 10 Ammonium hydroxide (28% aqueous solution) 8 to 18Oleic acid 18 to 40 Part B:

Sodium persulfate 15 to 35 Ammonium persulfate 4 to 10 Sodium sulfite0.005 to 0.1 Part C:

Sodium carbonate peroxide 10 to 25 Sodium sulfite 0.005 to 0.1 Part D:

Ammonium thiocyanate 0.4 to 1.1

Part E, which may also be part of the kit but is normally supplied bythe user, himself, is as follows:

Part E: Parts by weight Hydrogen peroxide (6% aqueous solution,

stabilized with phenacetin) 70 to The components of Part A aresequentially combined at room temperature but then, to facilitatereaction of the ammonium hydroxide and the oleic acid, or other higherfatty acid that may be used in partial replacement of the oleic acid,the temperature may be raised to as high as 40 C. When the materials arereacted and dissolved, the clear, golden, liquid solution is cooled toroom temperature and 0.2 to 2 parts of perfume are added, together withany other desired additives, e.g., dyes, thickeners, germicides. It isthen bottled. The Part B materials, all

powders, are mixed together and vacuum packed in foil envelopes,preferably weighed out in end use quantities that are recommended, andthe same is done for Part C. The catalyst is treated similarly (Part D).The peroxide solution (Part E) is a standard article of commerce, whichmay be re-bottled. The entire kit with or without the hydrogen peroxide,as desired, is boxed, ready for use.

In use, the desired proportions of the components are sequentiallymixed. First, Parts B, C and E are mixed together, with vigorous shakingfor about 30 seconds. Then, the catalyst, Part D, is added to Part A anddissolved therein. Finally, the two pre-mixes are blended, by shakingfor about seconds, forming a creamy colloidal bleach which is ready foruse immediately.

The bleach emulsion is applied to the hair roots about 4; inch deep soas to bleach the hair from the scalp to about 1 inch from it. The usualmethod for doing this is followed, parting the hair, applying bleach,combing the hair over, parting about an inch from the previous part, andrepeating the operations until bleach has been applied to all hairroots. As the components of the bleach react, while on the hair, thetemperature thereof increases to about 38 C., oxygen is graduallyreleased and the hair is satisfactorily bleached. Any iron present onthe hair or with the melanin pigment thereof, aids in releasing theoxygen and is also removed from the hair by the bleach. The pH of thehair is maintained in the range of 6.8 to 7.5 during the bleaching, dueto the balanced pH of the bleaching composition. Thus, when bleaching iscompleted, after to minutes, when the oxidizing capacity of the bleachis no longer significant, the hair bleached, although colorless andready for acceptance of dyes, is not damaged, as would be the case whenemploying more alkaline bleaches. The desired pH range of bleaching canbe modified by adjustment of the pH of the bleach composition,preferably by increasing or decreasing the proportions of ammoniumhydroxide and/or oleic acid in Part A. Also, if desired, other buffersmay be incorporated in the bleaches, e.g., citrates, silicates.

Of course, at the termination of the bleaching operation, which can bestopped at any convenient point before exhaustion of the bleachingcapacity of the composition, the hair is completely rinsed with waterand dried. A conditioning treatment may be effected at that time or thehair may be dyed to a desired shade. Dyeing may be effected after thehair is dried or while it is still damp from rinsing. The dyes applied,especially the paraphenylene dyes, take very well to the bleached hairand the dyed hair is soft and lustrous, not rough, split, broken orotherwise damaged.

Although good products are made throughout the ranges given, usually oneof skill in the art will know how to adjust the formula within theranges for best results and will do so in accordance with the presentteachings.

When the formulation is varied, as taught in the specification,equivalent results are obtained. Thus, when a higher alkoxy polyethoxyethanol, such as Neodol -11 (Shell Chemical Company), other Neodols andother Tritons or Igepals of this type are employed, good Wetting andcleaning action is also obtained without interfering with the bleachingeffects. When some of the oleic acid is replaced by lauric acid, up to30% of the acid content, the product is effective. The methanol may bereplaced partially or completely by isopropanol or ethanol, in thatorder of preference. Results are not as good with ethanol and it willusually be omitted. When the propylene glycol is replaced by a lowmolecular weight polyethylene glycol, of molecular weight of about 250or when a small amount of silicone or other commercial foam killer isused, foam volume is diminished. In a similar manner, the concentrationsof peroxide employed are changed, to 3% or 12%, with the quantity ofwater in the product being altered concomitantly. Triethanolamine may besubstituted for some of the ammonium thiocyanate. It has a catalyzingelfect on the per-compounds, causing desired release of oxygen, but isnot as good as the thiocyante. Of course, other thiocyanates, e.g.,sodium and potassium thiocyanates, and other per-compounds, e.g.,corresponding alkali metal salts, can be used and the products made willbe of good bleaching activities. However, the ranges described in thisexample and the compounds disclosed are considered to be for the bestproportions and materials to produce the most desired products.

EXAMPLE 2 Quantity employed (single bleach application) t-Octyl phenoxypolyethoxy ethanol (Triton X-) cc 10 Oleic acid cc 30 Oleyl alcohol cc 8Propylene glycol cc 3 Methanol cc 10 Ammonium hydroxide (28% aqueoussolution) cc 13 Sodium persulfate g 25 Ammonium persulfate g 7 Sodiumcarbonate peroxide g 18 Sodium sulfite g 0.1 Ammonium thiocyanate g 0.7Hydrogen peroxide (6% aqueous solution) cc The above components areadmixed in the manner described in Example 1. Before use, the productsinclude 10 parts nonionic detergent, 29 parts ammonium oleate, 7 partsoleyl alcohol, 3 parts propylene glycol, 8 parts methanol, 25 partssodium persulfate, 7 parts ammonium persulfate, 18 parts sodiumcarbonate peroxide, 0.1 part sodium sulfite, 0.7 part ammoniumthiocyanate, 123 parts water and 7.2 parts hydrogen peroxide. The bleachemulsion is tested for bleaching activity on a plurality of humansubjects of different hair shades, ranging from dark blonde to brunette.The bleach is employed in the final composition for both whole headbleaching and root bleaching of previously bleached hair. Quantitiesused range from 100 -to 300 cc. (cubic centimeters), being usually about230 cc. Bleaching is at a self-developed elevated temperature of 38 C.,although bleaching can also be effected at temperatures of 30 to 40 C.with this preparation. Bleaching times at the desired temperatures arefrom 20 to 30 minutes and with the particular described formula it is 25minutes. The bleached hair is strong, unsplit, smooth and shiny, notcoarse and damaged as is the case when a highly alkaline bleach is usedto release the oxygen from the peroxides and per-salts. (The presentbleach pH is adjusted to maintain about pH 7.2 on the hair.)

EXAMPLE 3 When the formula and procedures of Example 2 are followed,except that a stoichiometric equivalent of half the ammonia is replacedby sodium metasilicate, to supply needed alkalinity, and half theammonium thiocyanate is replaced by 2.5 g. of triethanolamine, to act asa catalyst and provide alkalinity, very good bleaching is effected.Similarly, when complete replacements of the ammonia and catalyst aremade by such materials, bleaching is obtained but it is considered to beinferior to that of the present compositions. If desired, the ammoniumthiocyanate or other suitable thiocyanate is used with only hydrogenperoxide or other per-compound mentioned herein or other suitableper-compound and it produces a regulated release of oxygen and promoteseven bleaching of the human hair, without detrimental effects associatedwith highly alkaline bleaching. Yet, depite this utility, for the bestcommercially acceptable compositions, the presently described preferredformulations should be employed.

The invention has been described with respect to illustrations andworking examples thereof but is not to, be considered as being solimited because it is clear that subsitutes and equivalents may beemployed within the spirit and scope of the described invention.

alkali metal carbonate peroxide, an alkali metal percar-' bonate, analkali metal persulfate, ammonium persulfate and mixtures thereof, about4 to 11 parts by Weight of hydrogen peroxide, about 100 to 150 parts byweight of water and about 0.4 to 1.1 parts by weight of a thiocyanatecatalyst selected from the group consisting of an alkali metalthiocyanate and ammonium thiocyanate having a pH in the range of 6.5 to8.5.

2. A method according to claim 1 wherein the bleaching composition alsocontains from about 20 to 45 parts by weight of an oleate soap and aboutto 15 parts by Weight of a synthetic organic nonionic detergent.

3. A method according to claim 2 wherein the oleate soap is ammoniumoleate, the synthetic organic nonionic detergent is a middle alkylphenoxy polyethoxy ethanol wherein the polyethoxy ethanol portion isabout 60 to 70%, the per-compound is a mixture of an alkali metalcarbonate peroxide, an alkali metal persulfate and ammonium persulfate,the thiocyanate catalyst is ammonium thiocyanate and the bleachingcomposition also contains from about 5 to 15 parts by weight of a loweralkanol selected from the group consisting of methanol, isopropanol andmixtures thereof.

4. A bleaching composition for human hair comprising about 29 to 70parts by Weight of a per-compound selected from the group consisting ofan alkali metal carbonate peroxide, an alkali metal percarbonate, analkali metal persulfate, ammonium persulfate and mixtures thereof, about4 to 11 parts by weight of hydrogen peroxide, about 100 to 150 parts byweight of water and about 0.4 to 1.1 parts by Weight of a thiocyanatecatalyst selected from the group consisting of an alkali metalthiocyanate and ammonium thiocyanate having a pH in the range of 6.5 to8.5.

5. A bleaching composition according to claim 4 comprising about to 25parts by Weight of an alkali metal carbonate peroxide, about 15 to 35parts by Weight of an alkali metal persulfate, about 4 to 10 parts byweight of ammonium persulfate, about 0.4 to 1.1 parts by weight ofammonium thiocyanate, about 4 to 11 parts by weight of hydrogen peroxideand about 100 to 150 parts by weight of water and the composition alsocontains about to 45 parts by weight of ammonium oleate, about 5 to 15parts by weight of a middle alkyl phenoxy polyethoxy ethanol nonionicdetergent, of which about 60 to 70% is polyethoxy ethanol, about 5 to 10parts by weight of oleyl alcohol and about 5 to 15 parts by weight of alower alkanol selected from the group consisting of methanol,isopropanol and mixtures thereof.

6. A bleaching composition according to claim 5, in the form of anaqueous emulsion having a pH in the range 10 of about 6.8 to 7.5,comprising 20 to 45 parts by weight of ammonium oleate, 5 to 15 parts byweight of t-octyl phenoxy polyethoxy ethanol, 5 to 10 parts by weight ofoleyl alcohol, 5 to 15 parts by weight of methanol, 10 to 25 parts byweight of sodium carbonate peroxide, 15 to 35 parts by weight of sodiumpersulfate, 4 to 10 parts by weight of ammonium persulfate, to parts byweight of water, 4 to 11 parts by weight of hydrogen peroxide, 04 to 1.1parts by weight of ammonium thiocyanate and, as an additionalconstituent, 1 to 5 parts by Weight of propylene glycol.

7. A bleaching composition according to claim 6 which comprises aboutthe following amounts of components:

Parts by weigh t-Octyl phenoxy polyethoxy ethanol 10 Ammonium oleate 29Oleyl alcohol 7 Propylene glycol 3 Methanol 8 Sodium carbonate peroxide18 Sodium persulfate 25 Ammonium persulfate 7 Hydrogen peroxide 7.2Water 123 Ammonium thiocyanate 0.7 and, as an additional constituent,0.1 part by weight of sodium sulfite.

References Cited UNITED STATES PATENTS 2,283,350 5/1942 Baum 424-623,378,444 4/1968 Swanson 424-62 3,190,803 6/1965 Vogt 424-62 3,206,3649/1965 Purlee 424-62 3,341,418 9/1967 Moses et a1 424-73 X 3,651,2093/1972 Cohen 424-62 FOREIGN PATENTS 859,276 1/1961 Great Britain 424--62940,799 6/ 1948 France 424-62 78,053 5/1955 Netherlands 424-62 OTHERREFERENCES Hackhs Chemical Dictionary, The Blakiston Co., Philadelphia,Pa. (1944), p. 784.

Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd ed., vol. 13,Interscience Publishers, New York (1967), pp. 370, 393 and 394.

ALBERT T. MEYERS, Primary Examiner V. C. CLARKE, Assistant Examiner US.Cl. X.R.

4Digest 3; 810.2, 11, 110, 111; 252186

